Fcc catalyst compositions containing boron oxide and phosphorus

ABSTRACT

A method of cracking a hydrocarbon feed under fluid catalytic cracking conditions includes adding FCC compatible inorganic particles having a first particle type including one or more boron oxide components and a first matrix component into a FCC unit and adding cracking microspheres having a second particle type including a second matrix component, a phosphorus component and 20% to 95% by weight of a zeolite component into the FCC unit.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.14/134,640, filed on Dec. 19, 2013, the contents of which areincorporated herein in their entirety.

TECHNICAL FIELD

The present invention relates to a fluid catalytic cracking catalyst andto a hydrocarbon catalytic cracking process using the catalyst. Moreparticularly, the invention relates to a fluid catalytic crackingcatalyst composition comprising one or more boron oxide and phosphoruscomponents for metals passivation.

BACKGROUND

Catalytic cracking is a petroleum refining process that is appliedcommercially on a very large scale. Catalytic cracking, and particularlyfluid catalytic cracking (FCC), is routinely used to convert heavyhydrocarbon feedstocks to lighter products, such as gasoline anddistillate range fractions. In FCC processes, a hydrocarbon feedstock isinjected into the riser section of a FCC unit, where the feedstock iscracked into lighter, more valuable products upon contacting hotcatalyst circulated to the riser-reactor from a catalyst regenerator.

It has been recognized that for a fluid catalytic cracking catalyst tobe commercially successful, it must have commercially acceptableactivity, selectivity, and stability characteristics. It must besufficiently active to give economically attractive yields, have goodselectivity towards producing products that are desired and notproducing products that are undesired, and it must be sufficientlyhydrothermally stable and attrition resistant to have a commerciallyuseful life.

Excessive coke and hydrogen are undesirable in commercial catalyticcracking processes. Even small increases in the yields of these productsrelative to the yield of gasoline can cause significant practicalproblems. For example, increases in the amount of coke produced cancause undesirable increases in the heat that is generated by burning offthe coke during the highly exothermic regeneration of the catalyst.Conversely, insufficient coke production can also distort the heatbalance of the cracking process. In addition, in commercial refineries,expensive compressors are used to handle high volume gases, such ashydrogen. Increases in the volume of hydrogen produced, therefore, canadd substantially to the capital expense of the refinery.

Improvements in cracking activity and gasoline selectivity of crackingcatalysts do not necessarily go hand in hand. Thus, a cracking catalystcan have outstandingly high cracking activity, but if the activityresults in a high level of conversion to coke and/or gas at the expenseof gasoline the catalyst will have limited utility. Catalytic crackingin current FCC catalysts is attributable to both the zeolite andnon-zeolite (e.g. matrix) components. Zeolite cracking tends to begasoline selective, while matrix cracking tends to be less gasolineselective.

In recent years, the oil refining industry has shifted to processing alarger quantity of residual (resid) and resid-containing feeds due tochanges in the price structure and availability of crude oil. Manyrefiners have been processing at least a portion of residual oil intheir units and several now run a full residual oil cracking program.Processing resid feeds can drastically alter yields of valuable productsin a negative direction relative to a light feed. Aside from operationaloptimizations, the catalyst has a large impact on product distribution.Several factors are important to resid catalyst design. It is highlyfavorable if the catalyst can minimize coke and hydrogen formation,maximize catalyst stability, and minimize deleterious contaminantselectivity due to metal contaminants in resid feedstocks.

Resid feeds typically contain contaminant metals including Ni, V, Fe,Na, Ca, and others. Resid FCC for converting heavy resid feeds with highNi and V contaminants constitutes the fastest growing FCC segmentglobally. Both Ni and V catalyze unwanted dehydrogenation reactions, butNi is an especially active dehydrogenation catalyst. Ni significantlyincreases H₂ and coke yields. In addition to taking part in unwanteddehydrogenation reactions, V comes with other major concerns as it ishighly mobile under FCC conditions and its interaction with the zeolitedestroys its framework structure, which manifests itself as increased H₂and coke yields, as well as lower zeolite surface area retention. Evensmall amounts (e.g., 1-5 ppm) of contaminant metals in the feedcumulatively deposited on the catalyst can result in high H₂ and cokeyields during FCC operation, if the catalyst does not feature anoptimized metals passivation system, which is a major concern for therefining industry.

Since the 1960s, most commercial fluid catalytic cracking catalysts havecontained zeolites as an active component. Such catalysts have taken theform of small particles, called microspheres, containing both an activezeolite component and a non-zeolite component in the form of a highalumina, silica-alumina (aluminosilicate) matrix. The active zeoliticcomponent is incorporated into the microspheres of the catalyst by oneof two general techniques. In one technique, the zeolitic component iscrystallized and then incorporated into microspheres in a separate step.In the second technique, the in situ technique, microspheres are firstformed and the zeolitic component is then crystallized in themicrospheres themselves to provide microspheres containing both zeoliticand non-zeolitic components. For many years a significant proportion ofcommercial FCC catalysts used throughout the world have been made by insitu synthesis from precursor microspheres containing kaolin that hadbeen calcined at different severities prior to formation intomicrospheres by spray drying. U.S. Pat. No. 4,493,902 (“the '902patent”), incorporated herein by reference in its entirety, disclosesthe manufacture of fluid cracking catalysts comprisingattrition-resistant microspheres containing high Y zeolite, formed bycrystallizing sodium Y zeolite in porous microspheres composed ofmetakaolin and spinel. The microspheres in the '902 patent contain morethan about 40%, for example 50-70% by weight Y zeolite. Such catalystscan be made by crystallizing more than about 40% sodium Y zeolite inporous microspheres composed of a mixture of two different forms ofchemically reactive calcined clay, namely, metakaolin (kaolin calcinedto undergo a strong endothermic reaction associated withdehydroxylation) and kaolin clay calcined under conditions more severethan those used to convert kaolin to metakaolin, i.e., kaolin claycalcined to undergo the characteristic kaolin exothermic reaction,sometimes referred to as the spinel form of calcined kaolin. Thischaracteristic kaolin exothermic reaction is sometimes referred to askaolin calcined through its “characteristic exotherm.” The microspherescontaining the two forms of calcined kaolin clay are immersed in analkaline sodium silicate solution, which is heated, until the maximumobtainable amount of Y zeolite is crystallized in the microspheres.

Fluid cracking catalysts which contain silica-alumina or aluminamatrices are termed catalysts with “active matrix.” Catalysts of thistype can be compared with those containing untreated clay or a largequantity of silica, which are termed “inactive matrix” catalysts. Inrelation to catalytic cracking, despite the apparent disadvantage inselectivity, the inclusion of aluminas or silica-alumina has beenbeneficial in certain circumstances. For instance when processing ahydrotreated/demetallated vacuum gas oil (hydrotreated VGO) the penaltyin non-selective cracking is offset by the benefit of cracking or“upgrading” the larger feed molecules which are initially too large tofit within the rigorous confines of the zeolite pores. Once “precracked”on the alumina or silica-alumina surface, the smaller molecules may thenbe selectively cracked further to gasoline material over the zeoliteportion of the catalyst. While one would expect that this precrackingscenario might be advantageous for resid feeds, they are, unfortunately,characterized as being heavily contaminated with metals such as nickeland vanadium and, to a lesser extent, iron. When a metal such as nickeldeposits on a high surface area alumina such as those found in typicalFCC catalysts, it is dispersed and participates as highly active centersfor the catalytic reactions which result in the formation of contaminantcoke (contaminant coke refers to the coke produced discretely fromreactions catalyzed by contaminant metals). This additional coke exceedsthat which is acceptable by refiners. Loss of activity or selectivity ofthe catalyst may also occur if the metal contaminants (e.g. Ni, V) fromthe hydrocarbon feedstock deposit onto the catalyst. These metalcontaminants are not removed by standard regeneration (burning) andcontribute to high levels of hydrogen, dry gas and coke and reducesignificantly the amount of gasoline that can be made.

U.S. Pat. No. 4,192,770 describes a process of restoring selectivity ofcracking catalysts which are contaminated with metals during catalyticcracking operations. The catalysts are restored by adding boron toeither to the fresh make-up catalyst or to the catalyst duringoperations. One problem with this approach is that boron is directlyplaced on the catalyst, which may negatively impact the catalystmaterial. In addition, such an approach addresses the problem after ithas occurred, by treating the catalyst after it has been contaminated.U.S. Pat. No. 4,295,955 utilizes a similar approach by restoringcatalyst that has been contaminated with metals. U.S. Pat. No. 4,295,955also shows in the examples that fresh catalyst can be treated with boronto attenuate residual metals on the fresh catalyst that contribute tothe undesirable yield of hydrogen. U.S. Pat. Nos. 5,5151,394 and5,300,215 disclose catalyst compositions comprising molecular sievematerials and a boron phosphate matrix. The Examples state that theaddition of boron phosphate to the matrix does not change the physicalproperties or attrition resistance, but the addition of boron phosphateproduced gasoline with higher octane in a cracking process. U.S. Pat.No. 4,403,199 discloses that adding additional phosphorus to a zeoliticFCC catalyst that has been contaminated by a metal such as nickel andvanadium. United States patent number further discloses that phosphoruscan be incorporated into a cracking process by itself or with otherpassivating agents such as boron.

While the aforementioned patents show the utility of boron compounds fortreating contaminated catalysts and attenuating residual metals oncatalyst materials, it would be desirable to provide materials thatallow the addition of boron to FCC processes and units under dynamic andvarying conditions. It also would be desirable to provide FCC processesand FCC catalyst compositions that can reduce coke and hydrogen yieldsfor a variety of FCC unit conditions and hydrocarbon feeds, for example,feeds containing high levels of transition metals, such as resid feeds.

SUMMARY

One aspect of the invention is directed to a fluid catalytic cracking(FCC) catalyst composition for cracking hydrocarbons. Variousembodiments are listed below. It will be understood that the embodimentslisted below may be combined not only as listed below, but in othersuitable combinations in accordance with the scope of the invention.

In embodiment one, the catalyst composition comprises: a first particletype comprising one or more boron oxide components and a first matrixcomponent and a second particle type having a composition different fromthe first particle type, the second particle type comprising a secondmatrix component, a phosphorus component and 20% to 95% by weight of azeolite component, wherein the first particle type and second particletype are mixed together.

Embodiment two is directed to a modification of catalyst compositionembodiment one, wherein the one or more boron oxide components arepresent in an amount in the range of 0.005% to 8% by weight of the FCCcatalyst composition.

Embodiment three is directed to a modification of catalyst compositionembodiment one or two, wherein the phosphorus component is present in anamount in the range of about 0.5% to 10.0% by weight on an oxide basis.

Embodiment four is directed to a modification of any of catalystcomposition embodiments one through three, wherein at least one of thefirst matrix component and the second matrix component are selected fromthe group consisting of kaolinite, halloysite, montmorillonite,bentonite, attapulgite, kaolin, amorphous kaolin, metakaolin, mullite,spinel, hydrous kaolin, clay, gibbsite (alumina trihydrate), boehmite,titania, alumina, silica, silica-alumina, silica-magnesia, magnesia andsepiolite.

Embodiment five is directed to a modification of any of catalystcomposition embodiments one through four, wherein the second particletype comprises an oxide selected from the group consisting of yttria,and a rare earth component selected from ceria, lanthana, praseodymia,neodymia, and combinations thereof.

Embodiment six is directed to a modification of any of catalystcomposition embodiments one through five, wherein the rare earthcomponent is lanthana, and the lanthana is present in a range of 0.5 wt.% to about 10.0 wt. % on an oxide basis based on the weight of the FCCcatalyst composition.

Embodiment seven is directed to a modification of any of catalystcomposition embodiments one through six, wherein the second particletype further comprises a transition alumina component present in a rangeof 1 wt. % to 35 wt. %.

Embodiment eight of the invention is directed to a modification of anyof catalyst composition embodiments one through seven, wherein thezeolite component is intergrown with the second matrix component.

Embodiment nine is directed to a modification of any of catalystcomposition embodiments one through eight, wherein the second particletype comprises microspheres obtained by forming rare earth-containingmicrospheres containing the second matrix component, the transitionalumina, the zeolite component intergrown within the second matrixcomponent, and yttria or a rare earth component, and further adding thephosphorus component to the rare earth-containing microspheres toprovide catalytic microspheres.

Embodiment ten is directed to a modification of any of catalystcomposition embodiments one through nine, wherein the phosphoruscomponent is in the range of 0.5 wt. % to about 10.0 wt. % P₂O₅ on anoxide basis.

Embodiment eleven is directed to a modification of any of catalystcomposition embodiments one through ten, wherein the rare-earthcomponent is selected from the group consisting of ceria, lanthana,praseodymia, and neodymia.

Embodiment twelve is directed to a modification of any of catalystcomposition embodiments one through eleven, wherein the rare earthcomponent is lanthana, and the lanthana is present in a range of 0.5 wt.% to about 10.0 wt. % on an oxide basis.

Embodiment thirteen is directed to a modification of any of catalystcomposition embodiments one through twelve, wherein the microsphere hasa phosphorus level of about 2-4 wt. % P₂O₅ on an oxide basis of the FCCcatalyst composition and the rare earth metal component is present in anamount of about 1-5 wt. % on an oxide basis of the FCC catalystcomposition.

Another aspect of the invention pertains to a method of cracking ahydrocarbon feed under fluid catalytic cracking conditions. Therefore,embodiment fourteen is directed to method comprising contacting thehydrocarbon feed with any of catalyst composition embodiment of onethrough twelve.

Embodiment fifteen is directed to a method comprising contacting thehydrocarbon feed with the catalyst composition of catalyst compositionembodiment thirteen.

Embodiment sixteen is directed to a method comprising adding FCCcompatible inorganic particles comprising one or more boron oxidecomponents and a first matrix component into a FCC unit and addingcracking microspheres comprising a second matrix component, a phosphoruscomponent and 20% to 95% by weight of a zeolite component into the FCCunit.

Embodiment seventeen is directed to a modification of method embodimentsixteen, wherein the one or more boron oxides present in the FCCcomposition is in the in the range of 0.005% to 8% by weight on an oxidebasis and the phosphorus content is present on the cracking microspheresin the range of 0.5% and 10.0% by weight on an oxide basis.

Embodiment eighteen is directed to a modification of method embodimentsixteen or seventeen, wherein the cracking microspheres further comprisean oxide selected from the group consisting of yttria, ceria, lanthana,praseodymia, neodymia, and combinations thereof.

Embodiment nineteen is directed to a modification of any of methodembodiments sixteen through eighteen, wherein the rare earth componentis lanthana, and the lanthana is present in a range of 0.5 wt. % toabout 10.0 wt. % on an oxide basis based on the weight of the FCCcatalyst composition.

Embodiment twenty is directed to a modification of any of methodembodiments sixteen through nineteen, wherein the cracking microspheresfurther comprise a transition alumina component present in a range of 1wt. % to 35 wt. %.

DETAILED DESCRIPTION

Before describing several exemplary embodiments of the invention, it isto be understood that the invention is not limited to the details ofconstruction or process steps set forth in the following description.The invention is capable of other embodiments and of being practiced orbeing carried out in various ways.

Each FCC unit has a unique capacity and hydrocarbon feed, which meansthat a variety of boron-containing catalyst materials containingdifferent amounts of boron are needed. For example, resid feeds havehigher metals content than other types of hydrocarbon feeds, which mayrequire more boron than other hydrocarbon feeds that have lower metalscontent. Furthermore, even in the same FCC unit, the catalyst in theunit degrades over time, and it may be desirable to increase or decreasethe amount of boron in the unit to address the metals content of aparticular process at a particular time. Also, the quality of thehydrocarbon feed can change over time, and some hydrocarbon feeds mayrequire a different boron content to handle the different metalscontent. Further, it would be desirable to provide processes in whichboron is not placed in direct contact with zeolite on the crackingmicrospheres when the boron is applied to the material that is added tothe unit. Such processes would avoid any negative interactions betweenboron and zeolite on the cracking microspheres. It would be desirable toprovide a boron-containing additive that could be used with a variety ofFCC catalyst compositions that could address metals content undervarious process conditions. In particular, it would be desirable toprovide a way of providing varied boron content to various FCC feeds byutilizing solid, inert, FCC compatible inorganic particle containingboron, which also avoids direct application of boron materials to thecracking microspheres.

Embodiments of the present invention provide a FCC catalyst composition,which uses one or more boron oxide components for metal, particularly,nickel passivation. The presence of boron oxide in a fluid catalyticcracking catalyst as a trapping/passivating material results in lowerhydrogen and coke yields when processing heavy hydrocarbons feeds,particularly resid feeds, contaminated with transition metals.Passivating or passivation refers to the ability of the boron componentto reduce or prevent the activity of deleterious metals (such as nickel)from negatively impacting the selectivity of the FCC process. Providedherein are FCC catalysts, methods of making FCC catalysts, and methodsof cracking hydrocarbon feeds.

One aspect of the invention relates to a fluid catalytic cracking (FCC)catalyst composition for cracking hydrocarbons, the FCC catalystcomposition comprising a non-zeolitic component, and one or more boronoxide components, the FCC catalyst composition effective to reduce cokeand hydrogen yields during cracking of hydrocarbons. Lowering hydrogenyields is beneficial in wet gas compressor-limited processes. In one ormore embodiments, the non-zeolitic material can include one or more ofmetakaolin, spinel, kaolin and mullite. The FCC catalyst composition istypically in the form of particles, more specifically as microspheres,which will be described further below.

The non-zeolitic material may also be referred to as matrix material, asdiscussed further below. In one embodiment of the invention, a FCCcatalyst composition comprises particles consisting essentially ofmatrix material and one or more boron oxides. This composition,consisting essentially of matrix material and one or more boron oxides,provides a first particle type. In one embodiment, this first particletype can be used together with existing FCC catalyst compositions toreduce coke and hydrogen yields during cracking processes. For example,the first particle type may be introduced into an FCC unit with a secondparticle type, the second particle type comprising a non-zeoliticcomponent, a transition alumina component, a zeolite component, and arare earth component. The second particle type contains phosphorus.

As an alternative to providing a first particle type and a secondparticle type, one or more boron oxides can be used in a FCC catalystcomposition comprising particles containing a non-zeolitic component, atransition alumina component, a zeolite component, and a rare earthcomponent. In this alternative approach, the boron and the active FCCcatalyst are incorporated into an all-in-one particle. This compositioncontains phosphorus. According to embodiments of the present invention,when present in the composition, the zeolite component is present in arange of 20% to 95% by weight based on the catalyst composition.

Thus, embodiments of the invention provide FCC catalyst compositionscomprising particles comprising a non-zeolitic component, and one ormore boron oxide components. Providing two separate particle typesallows boron oxide-containing particles to be added to a FCC catalystcomposition in the unit as needed to passivate feeds having high metalcontents. Thus, embodiments of the present invention provide FCCcatalyst compositions using boron oxide-modified particles, which,according to one or more embodiments, can be made by spray drying amixture of mullite, hydrous kaolin, and a suitable binder, for example,a silicate binder, and then modifying the particles with one or moreboron oxide components as described below. In one or more embodiments,the boron can be added during spray-drying. In embodiments in which thecatalyst composition comprises a single particle type containing boron,the particles may also include a transition alumina and a zeolite. Thezeolite can be added as separate particles to the composition duringspray drying, or the zeolite can be intergrown in the particlecomposition by the in situ crystallization of the zeolite. The particlesmay further include a rare earth component and a phosphorus component.Thus, in an embodiment of the invention, particles are provided whichcontain a non-zeolitic component, a zeolite, a transition alumina, arare earth component, one or more boron oxide components, and optionallya phosphorus component.

In an alternative embodiment, as noted above, a first microsphere typecomprises a non-zeolitic component and one or more boron oxidecomponents, and a second microsphere type comprising a non-zeoliticcomponent, a transition alumina, a zeolite, a rare earth component, and,a phosphorus component.

According to one or more embodiments, a catalyst composition is providedwhich exhibits higher performance in which a mobile boron oxide speciesprevents contaminant metals from interfering with catalyst selectivity,reducing coke and hydrogen yield and enhancing zeolite stability.According to one or more embodiments, the selectivity benefits of addingphosphorus result in enhanced metals passivation, particularly whenphosphorus is added to a catalyst that contains transition alumina. Inparticular, in addition to surface area stabilization, phosphorusaddition to a transition alumina-containing catalyst providessignificant benefits, including lower hydrogen and coke yield and higheractivity. Lowering hydrogen yields is beneficial in wet gascompressor-limited processes.

With respect to the terms used in this disclosure, the followingdefinitions are provided.

As used herein, the term “catalyst” or “catalyst composition” or“catalyst material” refers to a material that promotes a reaction.

As used herein, the term “fluid catalytic cracking” or “FCC” refers to aconversion process in petroleum refineries wherein high-boiling,high-molecular weight hydrocarbon fractions of petroleum crude oils areconverted to more valuable gasoline, olefinic gases, and other products.

“Cracking conditions” or “FCC conditions” refers to typical FCC processconditions. Typical FCC processes are conducted at reaction temperaturesof 450° to 650° C. with catalyst regeneration temperatures of 600° to850° C. Hot regenerated catalyst is added to a hydrocarbon feed at thebase of a rise reactor. The fluidization of the solid catalyst particlesmay be promoted with a lift gas. The catalyst vaporizes and superheatsthe feed to the desired cracking temperature. During the upward passageof the catalyst and feed, the feed is cracked, and coke deposits on thecatalyst. The coked catalyst and the cracked products exit the riser andenter a solid-gas separation system, e.g., a series of cyclones, at thetop of the reactor vessel. The cracked products are fractionated into aseries of products, including gas, gasoline, light gas oil, and heavycycle gas oil. Some heavier hydrocarbons may be recycled to the reactor.

As used herein, the term “feed” or “feedstock” refers to that portion ofcrude oil that has a high boiling point and a high molecular weight. InFCC processes, a hydrocarbon feedstock is injected into the risersection of a FCC unit, where the feedstock is cracked into lighter, morevaluable products upon contacting hot catalyst circulated to theriser-reactor from a catalyst regenerator.

As used herein, the term “resid” refers to that portion of crude oilthat has a high boiling point and a high molecular weight and typicallycontains contaminant metals including Ni, V, Fe, Na, Ca, and others. Thecontaminant metals, particularly Ni and V, have detrimental effects oncatalyst activity and performance. In some embodiments, in a resid feedoperation, one of Ni and V metals accumulate on the catalyst, and theFCC catalyst composition is effective to reduce the detrimental effectsof nickel and vanadium during cracking.

As used herein, the term “one or more boron oxide components” refers tothe presence of multiple species of boron oxide. For example, in one ormore embodiments, boron oxide components can include a boron oxide in atrigonal environment (e.g. BO₃) and in a tetrahedral oxygen environment(e.g. BO₄—). Differences in the chemical composition of the boron oxidespecies after reaction with FCC catalysts containing Ni and other metalscan be observed by peak changes in boron nuclear magnetic resonance (¹¹BNMR) analyses. It is believed that boron oxide can interact withtransition metals, such as Ni and V, and inhibit the dehydrogenationactivity of the transition metal by forming a metal-borate (e.g.Ni-borate) complex, which results in a reduction in coke and hydrogenyields during cracking of hydrocarbons. However, because boron oxide ismobile, the trapping mechanism is different than that of a transitionalumina.

As used herein, “particles” can be in the form of microspheres which canbe obtained by spray drying. As is understood by skilled artisans,microspheres are not necessarily perfectly spherical in shape.

As used herein, the term “non-zeolitic component” refers to thecomponents of a FCC catalyst that are not zeolites or molecular sieves.As used herein, the non-zeolitic component can comprise binder andfiller. The phrase “non-zeolitic component” may be used interchangeablywith the phrase “matrix material.” According to one or more embodiments,the “non-zeolitic component” can be selected from the group consistingof kaolinite, halloysite, montmorillonite, bentonite, attapulgite,kaolin, amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin,clay, gibbsite (alumina trihydrate), boehmite, titania, alumina, silica,silica-alumina, silica-magnesia, magnesia and sepiolite. According toone or more embodiments, the non-zeolitic component can be analuminosilicate.

As used herein, the term “molecular sieve” refers to a materialcomprising a framework based on an extensive three-dimensional networkof oxygen ions containing generally tetrahedral type sites. As usedherein, the term “zeolite” refers to a molecular sieve, which is acrystalline aluminosilicate with a framework based on an extensivethree-dimensional network of oxygen ions and have a substantiallyuniform pore distribution.

As used herein, the term “in situ crystallized” refers to the process inwhich a zeolite is grown or intergrown directly on/in a microsphere andis intimately associated with the matrix or non-zeolitic material forexample, as described in U.S. Pat. Nos. 4,493,902 and 6,656,347.“Transition alumina” is defined as any alumina which is intermediatebetween the thermodynamically stable phases of gibbsite, bayerite,boehmite, pseudoboehmite and nordstrandite on one end of the spectrumand alpha alumina or corundum on the other. Such transition aluminas maybe viewed as metastable phases. A scheme of the transformation sequencecan be found in the text: Oxides and Hydroxides of Aluminum by K. Wefersand C. Misra; Alcoa Technical Paper No. 19, revised; copyright AluminumCompany of America Laboratories, 1987.

As used herein, “cracking particle” refers to a particle which containsan active cracking component conventionally present to effect the moreselective hydrocarbon cracking reactions to provide more desiredproducts such as gasoline, propylene and LPG. Normally, the activecracking component to effect the more selective hydrocarbon crackingreactions comprises a molecular sieve such as a zeolite. The activecracking component is combined with a matrix material such as silica oralumina as well as a clay to provide the desired mechanicalcharacteristics such as attrition resistance. It is understood that thematrix material has some cracking activity, but matrix material is lessselective in cracking. As used herein, “FCC compatible inorganicparticle” is a particle that is less selective in providing the morevaluable products such as gasoline, propylene and LPG.

FCC catalyst compositions which include a zeolite component have acatalytically active crystallized aluminosilicate material, such as, forexample, a large-pore zeolite crystallized on or in a microspherecomprising non-zeolitic material. Large pore zeolite cracking catalystshave pore openings of greater than about 7 Angstroms in effectivediameter. Conventional large-pore molecular sieves include zeolite X;REX; zeolite Y; Ultrastable Y (USY); Rare Earth exchanged Y (REY); RareEarth exchanged USY (REUSY); Dealuminated Y (DeAl Y); Ultrahydrophobic Y(UHPY); and/or dealuminated silicon-enriched zeolites, e.g., LZ-210.According to one or more embodiments, the FCC catalyst comprisescracking microspheres comprising a crystalline aluminosilicate materialselected from zeolite Y, ZSM-20, ZSM-5, zeolite beta, zeolite L; andnaturally occurring zeolites such as faujasite, mordenite and the like,and a non-zeolitic component. These materials may be subjected toconventional treatments, such as calcinations and ion exchange with rareearths to increase stability.

As used herein, “mobile,” refers to the ability of boron to move withinand between particle types in the FCC unit.

Particles (e.g. microspheres) comprising hydrous kaolin clay and/ormetakaolin, a dispersible boehmite, optionally spinel and/or mullite,and a sodium silicate or silica sol binder can be prepared in accordancewith the techniques described in U.S. Pat. No. 6,716,338, which isincorporated herein by reference. For example, the catalysts can be madeby crystallizing the desired amount of sodium Y zeolite in porousmicrospheres composed of a mixture of two different forms of chemicallyreactive calcined clay, namely, metakaolin and spinel. The microspherescontaining the two forms of calcined kaolin clay are immersed in analkaline sodium silicate solution, which is heated, until the maximumobtainable amount of Y zeolite is crystallized in the microspheres. Theamount of zeolite according to embodiments of the invention is in therange of 20% to 95%, or 30% to 60%, or 30% to 45% by weight based on theweight of the FCC catalyst composition.

Preparation of Boron Oxide-Containing Particles

As described above, the FCC catalyst compositions can be providedutilizing first and second particle types. Alternatively, a FCC catalystcomposition can be provided wherein the boron can be incorporated into asingle particle type (an all-in-one particle—one or more boron oxidecomponents, nonzeolitic component, a zeolite component and optionallyone or more of a transition alumina component and a rare earthcomponent). In a FCC catalyst composition utilizing a single particletype, the boron can be incorporated in a variety of ways. In one or moreembodiments, the boron is placed on an all-in-one particle such that theboron is separated from the zeolite on the particle.

For example, boron oxide-containing particles can be prepared byimpregnating a matrix with boron. As used herein, the term “impregnated”means that a boron containing solution is put into pores of a material,such as a non-zeolitic component or a zeolite. In one or moreembodiments, particles are made utilizing the processes described inU.S. Pat. Nos. 5,559,067 and 6,716,338, as described further below inthe manufacture of the second particle type. Boron oxide can beincorporated during particle manufacture at various stages of theprocess. For example, boron oxide can be incorporated during particleformation such as during spray drying, after particle formation such asduring calcination or during ion exchange of the zeolite after theparticles are formed. One or more boron oxide components are present inan amount in the range of 0.005% and 8% by weight, including 0.005%,0.01%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.5%,2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5% and 7.0% byweight on an oxide basis based on the weight of the FCC catalystcomposition.

In one or more embodiments, one or more boron oxide components are mixedwith the non-zeolitic and spray dried to form the particles. In otherembodiments, one or more boron oxide components are spray loaded ontoFCC compatible inorganic particles. The loading can occur by a varietyof techniques such as impregnation, spray-coating, etc.

In still further embodiments, one or more boron oxide components areadded to non-zeolitic particles during calcination of the particles. Thespray dried particles are formed in the usual way, and the one or moreboron oxide components can be added during calcination.

In an alternative embodiment, boron can be added to the zeolitecontaining particles during ion exchange, as described further below.

Preparation of Catalyst Compositions Including First and Second ParticleTypes

As mentioned above, catalyst compositions can be provided utilizing afirst particle type consisting essentially of one or more boron oxidesand matrix material and a second particle type containing matrixmaterial, zeolite, transition alumina, and a rare earth component. Afirst particle type containing boron oxide can be prepared by mixing amatrix component (e.g. metakaolin, spinel, kaolin, mullite, etc.) withboron oxide. In accordance with the methods described in U.S. Pat. Nos.5,559,067 and 6,716,338, which are incorporated herein by reference,microspheres comprising one or more boron oxide components, and a matrixcomponent including hydrous kaolin clay, gibbsite (alumina trihydrate),spinel, and a silica sol binder, for example, an aluminum stabilizedsilica sol binder, are prepared by spray drying. It will be understoodthat the first particle type does not incorporate a zeolite andtherefore, a subsequent zeolite crystallization step is not utilized tomake the first particle type. The microspheres are calcined to convertthe hydrous kaolin component to metakaolin. The spray dried microspherescan be washed before calcination to reduce the sodium content if the solbinder contains a water soluble source of sodium, such as sodiumsulfate. One or more boron oxide components are then added and arepresent in an amount in the 0.005% and 8% by weight, including 0.005%,0.01%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.5%,2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5% and 7.0% byweight on an oxide basis based on the weight of the FCC catalystcomposition

Preparation of Second Particle Type

According to one or more embodiments, a second particle type is preparedby in situ techniques according to the processes established in U.S.Pat. No. 5,559,067 (the '067 patent) and U.S. Pat. No. 6,716,338 (the'338 patent), which are herein incorporated by reference in theirentireties. In general, the microspheres are first formed, and thezeolitic component is then crystallized in/on the microspheresthemselves to provide microspheres containing both zeolitic andnon-zeolitic components.

An aqueous slurry of finely divided hydrous kaolin, kaolin that has beencalcined through its characteristic exotherm, and binder is prepared.The slurry can optionally contain boehmite. In specific embodiments, thehydrous kaolin, calcined kaolin and binder are premixed in one tank andfed to the spray drier from one line. When present, an aqueous aluminaslurry, peptized such as with formic acid is introduced from a separateline immediately prior to when the whole mix enters the spray drier.Other mixing and injection protocols may also be useful. For example, apolymer dispersed alumina, for example dispersed with Flosperse® can beused in the process. The final slurry solids are about 30-70 wt. %. Theaqueous slurry is then spray dried to obtain microspheres comprising asilica bonded mixture of hydrated kaolin, kaolin that has been calcinedat least substantially through its characteristic exotherm (spinel, ormullite, or both spinel and mullite), and optionally boehmite.

The reactive kaolin of the slurry to form the microspheres can be formedof hydrated kaolin or calcined hydrous kaolin (metakaolin) or mixturesthereof as described in the '067 and '338 patents.

A commercial source of powdered kaolin calcined through the exotherm,may be used as the spinel component. Hydrated kaolin clay is convertedto this state by calcining the kaolin at least substantially completelythrough its characteristic exotherm under the conditions described inthe '338 patent. (The exotherm is detectable by conventionaldifferential thermal analysis, DTA.). After completion of calcination,the a calcined clay can be pulverized into finely divided particlesbefore being introduced into the slurry that is fed to a spray dryer.The spray dried product is repulverized. The surface area (BET) oftypical spinel form kaolin is low, e.g., 5-10 m²/g; however, when thismaterial is placed in a caustic environment such as that used forcrystallization, silica is leached, leaving an alumina-rich residuehaving a high surface area, e.g. 100-200 m²/g (BET).

Mullite can also be used as a matrix component. Mullite is made byfiring clay at temperatures above 2000° F. For example M93 mullite maybe made from the same kaolin clay, used for the preparation of spinelcomponent. Mullite can also be made from other kaolin clays. Mullite mayalso be made from Kyanite clay. Heating Kyanite clay to a hightemperature of 3000° F., provides a more crystalline, purer mullite inthe calcined product than that obtained from kaolin clay.

According to one or more embodiments, the alumina used to prepare themicrospheres is a highly dispersible boehmite. Dispersibility of thehydrated alumina is the property of the alumina to disperse effectivelyin an acidic media such as formic acid of pH less than about 3.5. Suchacid treatment is known as peptizing the alumina. High dispersion iswhen 90% or more of the alumina disperses into particles less than about1 micron. When this dispersed alumina solution is spray dried with thekaolin and binder, the resulting microsphere contains uniformlydistributed alumina throughout the microsphere.

After spray drying, the microspheres are washed and calcined at atemperature and for a time (e.g., for two to four hours in a mufflefurnace at a chamber temperature of about 1500° to 1550° F.) sufficientto convert the hydrated clay component of the microspheres tometakaolin, leaving the spinel component of the microspheres essentiallyunchanged. In specific embodiments, the calcined microspheres compriseabout 30 to 70% by weight metakaolin, about 10 to 50% by weight spineland/or mullite and 0.5 to about 20% by weight transition phase alumina.In one or more embodiments, the transition phase alumina comprises oneor more of eta, chi, gamma, delta or theta phase. In specificembodiments, the surface area (BET, nitrogen) of the crystallineboehmite (as well as the transition alumina) is below 150 m²/g,specifically below 125 m²/g, and more specifically, below 100 m²/g, forexample, 30-80 m²/g.

In one or more embodiments, the catalyst comprises from about 1% to 35%,or 5% to 25%, or 10% to 20% by weight of a transition alumina component(e.g. boehmite).

When microspheres contain a zeolite, precursor microspheres, which aremicrospheres obtained by calcining a non-zeolitic component and atransition alumina, are reacted with zeolite seeds and an alkalinesodium silicate solution, substantially as described in U.S. Pat. No.5,395,809, the teachings of which are incorporated herein bycross-reference. The microspheres are crystallized to a desired zeolitecontent (for example, 20-95% by weight, or 30-60% by weight, or 30-45%by weight), filtered, washed, ammonium exchanged, exchanged withrare-earth cations if required, calcined, exchanged a second time withammonium ions, and calcined a second time if required. The silicate forthe binder can be provided by sodium silicates with SiO₂ to Na₂O ratiosof from 1.5 to 3.5, more specifically, ratios of from 2.00 to 3.22.

In specific embodiments, the crystallized aluminosilicate materialcomprises from about 20 to about 95 wt. % zeolite Y, for example, 30% to60% by weight, or 30% to 45% by weight, expressed on the basis of theas-crystallized sodium faujasite form zeolite. In one or moreembodiments, the Y-zeolite component of the crystalline aluminosilicate,in their sodium form, have a crystalline unit cell size range of between24.64-24.73 Å, corresponding to a SiO₂/Al₂O₃ molar ratio of theY-zeolite of about 4.1-5.2.

After crystallization by reaction in a seeded sodium silicate solution,the microspheres contain crystalline Y-zeolite in the sodium form.Sodium cations in the microspheres are replaced with more desirablecations. This may be accomplished by contacting the microspheres withsolutions containing ammonium, yttrium cations, rare earth cations orcombinations thereof. In one or more embodiments, the ion exchange stepor steps are carried out so that the resulting catalyst contains lessthan about 0.7%, more specifically less than about 0.5% and even morespecifically less than about 0.4%, by weight Na₂O. After ion exchange,the microspheres are dried. Rare earth levels in the range of 0.1% to12% by weight, specifically 1-5% by weight, and more specifically 2-3%by weight are contemplated. More specifically, examples of rare earthcompounds are lanthana, ceria, praseodymia, and neodymia. Typically, theamount of rare earth added to the catalyst as a rare earth oxide willrange from about 1 to 5%, typically 2-3 wt. % rare earth oxide (REO). Ingeneral, the temperature of the impregnating solution will range fromabout 70-200° F. at a pH of from about 2-5.

Following ammonium and rare earth exchange, the microsphere catalystcomposition can optionally be further modified with phosphorus. Themicrosphere catalyst composition can be contacted with a mediumcontaining an anion, for example, a dihydrogen phosphate anion (H₂PO₄⁻), a dihydrogen phosphite anion (H₂PO₃ ⁻) or mixtures thereof for atime sufficient to composite phosphorus, with the catalyst. Suitableamounts of phosphorus to be incorporated in the catalyst include atleast about 0.5 weight percent, preferably at least about 0.7 weightpercent, more preferably from about 1 to 5 wt. %, calculated as P₂O₅,based on the weight of the zeolite plus whatever matrix remainsassociated with the zeolite.

The anion is derived from a phosphorus-containing component selectedfrom inorganic acids of phosphorus, salts of inorganic acids ofphosphorus, and mixtures thereof. Suitable phosphorus-containingcomponents include phosphorus acid (H₃PO₃), phosphoric acid (H₃PO₄),salts of phosphorus acid, salts of phosphoric acid and mixtures thereof.Although any soluble salts of phosphorus acid and phosphoric acid, suchas alkali metal salts and ammonium salts may be used to provide thedihydrogen phosphate or phosphite anion, in specific embodiments,ammonium salts are used since the use of alkali metal salts wouldrequire subsequent removal of the alkali metal from the catalyst. In oneembodiment, the anion is a dihydrogen phosphate anion derived frommonoammonium phosphate, diammonium phosphate and mixtures thereof.Contact with the anion may be performed as at least one step ofcontacting or a series of contacts which may be a series of alternatingand successive calcinations and dihydrogen phosphate or phosphite anioncontacting steps. In specific embodiments, up to about 3-4% P₂O₅ contentis achieved in a single step.

Contact of the anion with the zeolite and kaolin derived matrix issuitably conducted at a pH ranging from about 2 to about 8. The lower pHlimit is selected to minimize lass of crystallinity of the zeolite. Theupper pH limit appears to be set by the effect of the anionconcentration. Suitable concentrations of the dihydrogen phosphate ordihydrogen phosphite anion in the liquid medium range from about 0.2 toabout 10.0 weight percent anion.

In the above described procedure, the rare earth ion exchange isperformed prior to addition of the phosphorus component. However, itwill be understood that according to one or more embodiments, it may bedesirable to add the phosphorus component prior to rare earth ionexchange.

According to one or more embodiments, the catalyst comprises from about1% to about 5% phosphorus (P₂O₅), including 1, 2, 3, 4, and 5%. Inspecific embodiments, the catalyst comprises at least 1% P₂O₅.Subsequent to the rare earth exchange and phosphorus addition, catalystcomposition in the form of microspheres is dried and then calcined at atemperature of from 800°−1200° F. The conditions of the calcination aresuch that the unit cell size of the zeolite crystals is notsignificantly reduced. Typically, the drying step, after rare earthexchange is to remove a substantial portion of the water containedwithin the catalyst, and calcination is conducted in the absence ofadded steam. The rare earth oxide-containing catalyst, subsequent tocalcination, is now further acid exchanged, typically by ammonium ionsto, again, reduce the sodium content to less than about 0.5 wt. % Na₂O.The ammonium exchange can be repeated to ensure that the sodium contentis reduced to less than 0.5 wt. % Na₂O. Typically, the sodium contentwill be reduced to below 0.2 wt. % as Na₂O. Subsequent to ammoniumexchange, the reduced sodium catalyst containing the Y-type zeolite andthe kaolin derived matrix can be contacted again with a mediumcontaining the phosphorus compounds as described above, with respect tothe first phosphorus treatment. The medium contains sufficientphosphorus to provide a content of phosphorus as P₂O₅ of at least 0.5wt. % and up to 10.0 wt. %, typically 2.0 wt. % to 4.0 wt. % and, moretypically, an amount of phosphorus as P₂O₅ of 2.8 to 3.5 wt. % relativeto the catalyst, including zeolite and kaolin derived matrix.Temperatures and pH conditions for the second phosphorus treatment areas in the first treatment described above. After phosphorus treatment,the impregnated catalyst is calcined again at temperatures of from700°−1500° F.

The catalysts of the invention can also be used in conjunction withadditional V-traps. Thus, one or more embodiments, the catalyst furthercomprises a V-trap. The V-trap can be selected from one or moreconventional V-traps including, but not limited to, MgO/CaO. Withoutintending to be bound by theory, it is thought that MgO/CaO interactswith V₂O₅ through an acid/base reaction to give vanadates.

Another aspect of the present invention is directed to a method ofcracking a hydrocarbon feed under fluid catalytic cracking conditions.In one or more embodiments, the method comprises contacting thehydrocarbon feed with the boron oxide containing FCC catalystcomposition of one or more embodiments. In one or more embodiments, thehydrocarbon feed is a resid feed. In one or more embodiments, in a residfeed operation, one of Ni and V metals accumulate on the catalyst, andthe FCC catalyst composition is effective to reduce the detrimentaleffects of nickel and vanadium during cracking, thus reducing coke andhydrogen yields.

Conditions useful in operating FCC units utilizing catalyst of theinvention are known in the art and are contemplated in using thecatalysts of the invention. These conditions are described in numerouspublications including Catal. Rev.—Sci. Eng., 18 (1), 1-150 (1978),which is herein incorporated by reference in its entirety. The catalystsof one or more embodiments are particularly useful in cracking residuumand resid-containing feeds.

A further aspect of the present invention is directed to a method ofmanufacturing a FCC catalyst composition. In one or more embodiments,the method comprises forming particles containing a non-zeoliticcomponent and one or more boron oxides. The one or more boron oxides canbe impregnated onto the particles. Alternatively, the boron can beincorporated during spray drying, or using other techniques such ascoating, etc.

In one or more embodiments, the one or more boron oxides are mixed withthe non-zeolitic component and spray dried to form the particles. Inother embodiments, the one or more boron oxides are loaded ontonon-zeolitic particles. In still further embodiments, the one or moreboron oxides are added to FCC compatible inorganic particles duringcalcination of the particles.

In some embodiments, the non-zeolitic material includes metakaolin,kaolin, mullite, spinel, and combinations thereof. The particle canfurther comprise a transition alumina, a rare earth component, and amolecular sieve or zeolite component intergrown in situ with theparticles, as described in U.S. Pat. Nos. 4,493,902 and 6,656,347. Inone or more embodiments, one or more boron oxides are added to theparticles including intergrown molecular sieve or zeolite during ionexchanges. According to one or more embodiments, the molecular sieve orzeolite and matrix can also be made using conventional techniques formixing molecular sieves and matrix materials. For example, zeolite ormolecular sieve components can be dry blended or wet ball milledtogether, and then added to a suitable matrix and further mixed. Thematrix and zeolite mixture can be extruded, pilled, dropped in an oilbath, etc. to form relatively large particles. For use in fluidized bedcatalytic cracking units the matrix-zeolite mixture can be spray dried,but any other means can be used to make fluidizable catalyst particles,such as crushing or grinding larger size extrudates or pills.

The invention is now described with reference to the following examples.

EXAMPLES Example 1—Comparative

Calcined kaolin (mullite) (36.6 kg) slurry made to 49% solids was addedto 59% solids hydrous kaolin (25.9 kg), while mixing, using a Cowlesmixer. Next, a 56% solids boehmite alumina (14 kg) slurry was slowlyadded to the mixing clay slurry and was allowed to mix for more thanfive minutes. The mixture was screened and transferred to a spray dryerfeed tank. The clay/boehmite slurry was spray dried with sodium silicateinjected in-line just prior to entering the atomizer. Sodium silicate(20.2 kg, 3.22 modulus) was used at a metered ratio of 1.14 liter/minslurry:0.38 liter/min silicate. The target particle size for themicrospheres was 80 microns. Binder sodium was removed from the formedmicrospheres by slurrying the microspheres for thirty minutes andmaintaining the pH from 3.5-4 using sulfuric acid. Finally, the acidneutralized microspheres were dried and calcined at 1350-1500° F. fortwo hours. The microspheres were processed to grow 60-65% zeolite Yusing an in situ crystallization process. A sample of crystallized NaYmicrospheres (250 g) was ion exchanged to achieve a Na₂O of 2.0% usingammonium nitrate. Rare earth (lanthanum) was then added to 2 wt. % REO.The rare earth exchanged sample was calcined at 1000° F. for 2 hours tostabilize the catalyst and facilitate zeolitic sodium removal. Aftercalcinations, a series of ammonium nitrate ion exchanges was performedto <0.2 wt. % Na₂O. Finally, with the reduced sodium, a secondcalcination was done at 1100° F. for 2 hours in order to furtherstabilize the catalyst and reduce unit cell size. The catalystcomposition is further impregnated with 3000 ppm each of nickel andvanadium and aged under cyclic reducing and oxidizing conditions in thepresence of steam at between 1350-1500° F. The catalytic activity andselectivity of the catalyst composition is determined using AdvancedCracking Evaluation (ACE) reactors and protocols.

Example 2—Comparative

A catalyst composition as described in Example 1 was prepared.

Particles comprising matrix material and 7 wt. % boron oxide wereprepared, and these particles were mixed with the catalyst compositiondescribed in Example 1 in a ratio of 5% boron oxide particles and 95% ofthe catalyst composition of Example 1 to provide a catalyst compositioncomprising 0.35 wt. % of a boron component on an oxide basis.

Example 3—Comparative

Calcined kaolin (mullite) (36.6 kg) slurry made to 49% solids was addedto 59% solids hydrous kaolin (25.9 kg), while mixing, using a Cowlesmixer. Next a 56% solids boehmite alumina (14 kg) slurry was slowlyadded to the mixing clay slurry and was allowed to mix for more thanfive minutes. The mixture was screened and transferred to a spray dryerfeed tank. The clay/boehmite slurry was spray dried with sodium silicateinjected in-line just prior to entering the atomizer. Sodium silicate(20.2 kg, 3.22 modulus) was used at a metered ratio of 1.14 liter/minslurry:0.38 liter/min silicate. The target particle size for themicrospheres was 80 microns. Binder sodium was removed from the formedmicrospheres by slurrying the microspheres for thirty minutes andmaintaining the pH from 3.5-4 using sulfuric acid. Finally, the acidneutralized microspheres were dried and calcined at 1350-1500° F. fortwo hours. The microspheres were processed to grow 60-65% zeolite Yusing an in situ crystallization process. A sample of crystallized NaYmicrospheres (250 g) was ion exchanged to achieve a Na₂O of 2.0% usingammonium nitrate. The sodium adjusted sample was treated with phosphorusto 1.5% P₂O₅. Rare earth (lanthanum) was then added to 2 wt. % REO. Thephosphorus and rare earth exchanged sample was calcined at 1000° F. for2 hours to stabilize the catalyst and facilitate zeolitic sodiumremoval. After calcinations, a series of ammonium nitrate ion exchangeswas performed to <0.2 wt. % Na₂O. Once at desired sodium level, a secondphosphorus treatment was carried out to increase the total P₂O₅ to 3%.Finally, with the reduced sodium, a second calcination was done at 1100°F. for 2 hours in order to further stabilize the catalyst and reduceunit cell size. The catalyst composition is further impregnated with3000 ppm each of nickel and vanadium and aged under cyclic reducing andoxidizing conditions in the presence of steam at between 1350-1500° F.The catalytic activity and selectivity of the catalyst composition isdetermined using Advanced Cracking Evaluation (ACE) reactors andprotocols.

Example 4

A catalyst composition as described in Example 3 was prepared. Particlescomprising matrix material and 7 wt. % boron oxide were prepared, andthese particles were mixed with the catalyst composition described inExample 3 in a ratio of 5% boron oxide particles and 95% of the catalystcomposition of Example 3 to provide a catalyst composition comprising0.35 wt. % of a boron component on an oxide basis.

Activity @ ZSAR % Hydrogen Coke Gasoline 7.7 Cat Oil Comp. 66 0.81 13.4942.59 3.57 Example 1 Comp. 60 0.59 10.44 46.30 3.76 Example 2 Comp. 700.56 11.87 43.94 4.75 Example 3 Example 4 66 0.49 11.05 44.82 4.35

A comparison of Examples 1 and 2 reveals that the addition of oxides ofboron reduces hydrogen and coke yields but also decreases zeolitesurface area retention and activity. The addition of phosphorous,Example 3 and 4 improves the zeolite surface area retention and thecombination with oxides of boron (Example 4) shows both high activityand low hydrogen and coke yields. Thus, the combination of oxides ofboron and catalyst modification with phosphorous to a starting catalystformulation, comparison of Example 1 and 4, yields dramatic decreases inhydrogen and coke while maintaining high activity and zeolite surfacearea retention.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference for allpurposes to the same extent as if each reference were individually andspecifically indicated to be incorporated by reference and were setforth in its entirety herein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the materials and methods discussed herein(especially in the context of the following claims) are to be construedto cover both the singular and the plural, unless otherwise indicatedherein or clearly contradicted by context. Recitation of ranges ofvalues herein are merely intended to serve as a shorthand method ofreferring individually to each separate value falling within the range,unless otherwise indicated herein, and each separate value isincorporated into the specification as if it were individually recitedherein. All methods described herein can be performed in any suitableorder unless otherwise indicated herein or otherwise clearlycontradicted by context. The use of any and all examples, or exemplarylanguage (e.g., “such as”) provided herein, is intended merely to betterilluminate the materials and methods and does not pose a limitation onthe scope unless otherwise claimed. No language in the specificationshould be construed as indicating any non-claimed element as essentialto the practice of the disclosed materials and methods.

Reference throughout this specification to “one embodiment,” “certainembodiments,” “one or more embodiments” or “an embodiment” means that aparticular feature, structure, material, or characteristic described inconnection with the embodiment is included in at least one embodiment ofthe invention. Thus, the appearances of the phrases such as “in one ormore embodiments,” “in certain embodiments,” “in one embodiment” or “inan embodiment” in various places throughout this specification are notnecessarily referring to the same embodiment of the invention.Furthermore, the particular features, structures, materials, orcharacteristics may be combined in any suitable manner in one or moreembodiments.

Although the invention herein has been described with reference toparticular embodiments, it is to be understood that these embodimentsare merely illustrative of the principles and applications of thepresent invention. It will be apparent to those skilled in the art thatvarious modifications and variations can be made to the method andapparatus of the present invention without departing from the spirit andscope of the invention. Thus, it is intended that the present inventioninclude modifications and variations that are within the scope of theappended claims and their equivalents.

What is claimed is:
 1. A method of cracking a hydrocarbon feed underfluid catalytic cracking conditions, the method comprising adding FCCcompatible inorganic particles comprising a first particle typecomprising one or more boron oxide components and a first matrixcomponent into a FCC unit and adding cracking microspheres comprising asecond particle type comprising a second matrix component, a phosphoruscomponent and 20% to 95% by weight of a zeolite component into the FCCunit.
 2. The method of claim 1, wherein the one or more boron oxidespresent in the FCC composition is in the in the range of 0.005% to 8% byweight on an oxide basis and the phosphorus content is present on thecracking microspheres in the range of 0.5% and 10.0% by weight on anoxide basis.
 3. The method of claim 2, wherein the cracking microspheresfurther comprise a rare earth component selected from the groupconsisting of yttria, ceria, lanthana, praseodymia, neodymia, andcombinations thereof.
 4. The method of claim 3, wherein the rare earthcomponent is lanthana, and the lanthana is present in a range of 0.5 wt.% to about 10.0 wt. % on an oxide basis based on the weight of the FCCcatalyst composition.
 5. The method of claim 4, wherein the crackingmicrospheres further comprise a transition alumina component present ina range of 1 wt. % to 35 wt. %.
 6. The method of claim 1, wherein thefirst particle type does not incorporate a zeolite.
 7. The method ofclaim 1, wherein the one or more boron oxide components are present inan amount in the range of 0.005% to 8% by weight of the FCC catalystcomposition.
 8. The method of claim 1, wherein the phosphorus componentis present in an amount in the range of about 0.5% to 10.0% by weight ofthe second particle type on an oxide basis.
 9. The method of claim 1,wherein at least one of the first matrix component and the second matrixcomponent comprises at least one of member of the group consisting ofkaolinite, halloysite, montmorillonite, bentonite, attapulgite, kaolin,amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin, clay,gibbsite (alumina trihydrate), boehmite, titania, alumina, silica,silica-alumina, silica-magnesia, magnesia, and sepiolite.
 10. The methodof claim 9, wherein the second particle type further comprises atransition alumina component present in a range of 1 wt. % to 35 wt. %.11. The method of claim 10, wherein the zeolite component is intergrownwith the second matrix component.
 12. The method of claim 11, whereinthe second particle type comprises microspheres obtained by forming rareearth-containing microspheres containing the second matrix component,the transition alumina, the zeolite component intergrown within thesecond matrix component, an oxide selected from the group consisting ofyttria, and a rare earth component selected from ceria, lanthana,praseodymia, neodymia, and combinations thereof, and further adding thephosphorus component to the rare earth-containing microspheres toprovide catalytic microspheres.
 13. The method of claim 12, wherein thephosphorus component is in the range of 0.5 wt. % to about 10.0 wt. %P₂O₅ on an oxide basis.
 14. The method of claim 13, wherein therare-earth component is selected from the group consisting of ceria,lanthana, praseodymia, and neodymia.
 15. The method of claim 14, whereinthe rare earth component is lanthana, and the lanthana is present in arange of 0.5 wt. % to about 10.0 wt. % on an oxide basis.
 16. The methodof claim 15, wherein the microsphere has a phosphorus level of about 2-4wt. % P₂O₅ on an oxide basis of the FCC catalyst composition and therare earth metal component is present in an amount of about 1-5 wt. % onan oxide basis of the FCC catalyst composition.